JP2003523468A - Modified polyurethane foam used as an adsorbent - Google Patents

Abstract

The invention relates to polyurethane foams comprising(i) ethylenimine, polyethylenimine, polyvinylamine, polyvinylamine copolymers, carboxymethylated polyethylenimines, phosphonomethylated polyethylenimines, quarternized polyethylenimines and/or dithiocarbamatized polyethylenimines or(ii) alkali hydroxides and/or alkaline earth metal hydroxides ora mixture consisting of both (i) and (ii).

Description

Detailed Description of the Invention

The present invention relates to (i) ethyleneimine, polyethyleneimine, polyvinylamine,
Containing polyvinylamine-copolymer, carboxymethylated polyethyleneimine, phosphonomethylated polyethyleneimine, quaternized polyethyleneimine and / or dithiocarbamated polyethyleneimine, or (ii) alkali metal hydroxide or alkaline earth metal hydroxide Polyurethane foams, such as soft foams, semi-rigid foams or rigid foams, preferably open cell foams, their use and processes for their production.

The production of polyurethane foams (hereinafter also referred to as PUR-foams) by reacting polyisocyanates with compounds having at least two reactive hydrogen atoms has been known for a long time and described in many ways. It had been.

On the basis of the advantageous properties of PUR foams, these foams are in principle particularly suitable as active substance carrier materials, for example in terms of their slight wear and their chemical resistance. The loading of the active substance on the polymer offers the advantage of heterogeneous reactions in physical as well as in chemical methods compared to unsupported methods. This belongs to the possibilities for use in recycling and continuous flow processes, for example by simple removal and recovery of compounds, for example simple filtration or regeneration, and high effectiveness limited by the large surface area of the support material.

[0004] For example, WO 95/18159 describes the production of ion-exchange materials based on polyurethane foam, the ion-exchange materials being already added to the starting materials for the production of foams. Or later polymerized on the foam. A large number of polymers have been mentioned as ion exchange materials, especially polystyrene-polyethyleneimine. The use of polystyrene-polyethyleneimine is disadvantageous for two reasons. On the one hand, polyethyleneimine must first be combined with polystyrene in an additional working step. On the other hand, the amount of active substance effectively taken up by polystyrene, which is not suitable as active substance, is lower than in the case of direct use of polyethyleneimine.

Odorants are usually mixtures of organic substances, which already lead to considerable odor annoyance at specific low concentrations. A large number of sorbents are provided for this odor separation, for example activated carbon, silica gel, ban earth or molecular sieves can be used. Generally, these sorbents are supported on a polymeric backbone material such as foam.

JP 03009950 describes a deodorant polyurethane foam material which binds a large number of odorous substances. As the deodorizing component, for example, compounds based on phosphoric acid, phosphorous acid, hypophosphorous acid, hydrochloric acid and salts thereof (alkaline earth metal salts and alkali metal salts) are used. In addition, the active substance is preferably applied on a carrier (silica or alumina).

US Pat. No. 4,877,816 describes a foam cloth containing fine particles of a deodorant and a disinfectant. Zinc carbonate or iron sulfate is described as a deodorant, and phthalimide is described as a disinfectant. Preferably, polyurethane foam is used.

JP 49131986 discloses a polyurethane foam impregnated with a solution or suspension of a metal compound. Subsequently, these compounds are treated with alkaline, oxidizing or reducing compounds in order to produce metals, metal oxides or metal complexes on the foam. Foams can be used for odor adsorption.

JP 09057050 describes a deodorizing filter made of a polyurethane foam material containing an active substance such as activated carbon, an ion exchange resin, or a catalyst.

The object of the present invention was to develop polymers having an excellent adsorption capacity for various compounds, in particular heavy metal ions and dyes. Moreover, the foams produced should also be suitable for the adsorption of anionic heavy metal complexes, anionic organic molecules (eg: aldehydes or acids) and for cleaning papermaking wastewater.

Furthermore, the object of the invention was to develop a foam material which reliably and rapidly depletes odorous substances, and which is then preferably not passed through by the gas containing odorous substances.

The subject of the invention could be solved by a polyurethane foam containing compounds (i) and / or (ii).

The subject of the present invention is therefore (i) ethyleneimine, polyethyleneimine, polyvinylamine, polyvinylamine-copolymers, carboxymethylated polyethyleneimines, phosphonomethylated polyethyleneimines, quaternized polyethyleneimines and / or dithiocarbamates. A polyurethane foam comprising polyethyleneimine or (ii) an alkali metal hydroxide and / or an alkaline earth metal hydroxide or a mixture of (i) and (ii).

Another subject of the invention is the process for the production of the polyurethane foams according to the invention and their use for the adsorption of odorants and for the production of shaped bodies.

As compound (i), according to the invention, ethyleneimine, polyethyleneimine, polyvinylamine, polyvinylamine-copolymer, carboxymethylated polyethyleneimine, phosphonomethylated polyethyleneimine, quaternized polyethyleneimine and / or dithiocarbamate are used. Polyethyleneimine is used.

For example, the following applies: ethyleneimine, 500-800000 g /
Polyethyleneimine having an average molecular weight of mol, 1000 to 100000 g / mol
Carboxymethylated polyethyleneimine having an average molecular weight of 1000 to 10
Phosphonomethylated polyethyleneimine having an average molecular weight of 0000 g / mol,
Quaternized polyethyleneimine having an average molecular weight of 1000 to 250,000 g / mol, dithiocarbamate polyethyleneimine having an average molecular weight of 1000 to 250,000 g / mol, polyvinylamine having an average molecular weight of 1000 to 1500000 g / mol, 1000 to 2500000 g / mol Polyvinylamine-copolymer having an average molecular weight of In this case, all the descriptions are based on the number average molecular weight.

Preferably, (i) is polyethyleneimine and / or polyvinylamine.

As alkali metal hydroxides or alkaline earth metal hydroxides (ii) according to the invention, sodium hydroxide and potassium hydroxide are preferred.

In addition to adsorbing heavy metal ions and odorants, the foams produced are also suitable for adsorbing dyes, anionic heavy metal complexes or anions. Additionally, the foam material can be used for the adsorption of organic molecules (eg: aldehydes), for the cleaning of papermaking wastewater, or for the fixation of acid gases.

The production of the polyurethane foam according to the invention is carried out by reacting a polyisocyanate with a compound having at least two hydrogen atoms which is reactive with isocyanate, the compound (i) or (ii) being It is applied on the surface of foam. Compounds (i) and (ii) can be applied onto polyurethane foam by two preferred methods.

On the one hand, the production of polyurethane foams may be carried out by reacting a polyisocyanate with a compound having at least two hydrogen atoms reactive with isocyanate in the presence of (i) or (ii). it can. However, it is also possible to produce prepolymers from compound (i) by reaction with isocyanates. This is understood to be the reaction product of compound (i), which preferably has free isocyanate groups at the chain ends, and a polyisocyanate. Prepolymers and quasi-prepolymers and their preparation are generally known.

On the other hand, the polyurethane foam is, after its production, the compound (i) or (ii)
Can be impregnated with a solution of By impregnating the foam into the liquid compound (i) or with a solution of the solid or liquid compound (i) or (ii) in a suitable solvent,
(I) or (ii) is impregnated on the foam material. Suitable solvents are protic solvents such as water, acetone, ethanol, isopropanol, methyl ethyl ketone or halogen alkanes such as 1,2-dichloromethane. From the foam impregnated with compound (i) or (ii), the solvent can subsequently be separated off. This can be done by applying a vacuum or by drying at temperatures up to 50 ° C. By heat treatment at a temperature of 50 to 150 ° C. for a period of 4 to 72 hours, compound (i) can be reacted on the foam and covalently bound thereto.

Furthermore, the loading of compound (i) or (ii) can be carried out, for example, by spraying. The solvent still has to be removed in this case. This can be done, for example, by applying a vacuum and / or temperature.

During the subsequent impregnation of the foam with the solution of the compound (i) or (ii), the absorption capacity of the foam also depends on the type and polarity of the solvent in which the active substance is dissolved. Notably, the use of acetone as the preferred solvent for compound (i) enhances the capacity of the foam of (i). For compound (ii) alcohols, eg ethanol are preferably used.

The compound (i) or (ii) applied on the foam by impregnation can optionally be crosslinked on the foam in a further step. Suitable cross-linking agents are generally known, for example non-volatile PEG-bisglycidyl ether or polycarboxylic acids, for example tetracarboxylic acids. The temperatures required for crosslinking are 80 ° C for ethers and 120-130 ° C for polycarboxylic acids.

For better immobilization of the compound (i), foam materials with an isocyanate excess can be produced--in this case, the compound (i) forms a foam skeleton via the residual isocyanate groups. Can be fixed to.

The polyurethane foam according to the present invention preferably has a content of 0 based on the mass of the foam.
． It has a content of (i) or (ii) or a mixture of (i) and (ii) with a content of 1-80% by weight, preferably 20-70% by weight, particularly preferably 25-60% by weight.

The polyurethane foam according to the invention is preferably used in adsorbing odorants and heavy metal ions and dyes from liquids. However, the foam material can also be used for the adsorption of anionic heavy metal complexes, anions, acidic compounds and organic substances such as formaldehyde. Foams can likewise be used for cleaning papermaking wastewater. Foams can likewise be used for gas scrubbing, for example as ozone filters in passenger cars.

Hazardous substances, especially heavy metal ions and dyes, which can be preferably adsorbed by the polyurethane foams according to the invention become apparent from the choice of supported complexing agents. Some heavy metals, especially mercury and lead, are also adsorbed by the polyurethane foam, which causes an additional increase in impairment. Depending on the active substance carried,
Especially copper, nickel, cobalt, cadmium, mercury, lead, chromium, manganese, iron,
Rhenium, silver and zinc are adsorbed.

Suitable liquids from which harmful substances can be adsorbed are in principle all liquids in which these harmful substances are soluble and do not destroy the polyurethane foam matrix. Particularly suitable are water, optionally polar, water-miscible organic solvents as well as any mixtures of the compounds mentioned. In the case of aqueous solutions, the organic solvent content should preferably be less than 30% by weight, based on the weight of the solution, because otherwise partial segregation may occur during adsorption. Without
This causes interference during adsorption.

Preferably, the liquid containing the harmful substance is contacted with the polyurethane foam according to the invention containing (i). The polyurethane foam is then introduced into the liquid as a geometrically shaped body, for example as a cube or sphere, or in the form of agglomerates, in which it is stirred and, after adsorption, removed again using, for example, filtration. Can be done. In another embodiment of the invention, the polyurethane foam can be fixed, for example in a tube or a cartridge, and the liquid can be conducted to this fixed foam. The fixing of the foam can take place in an exchanger column, for example as a fixed bed. It has proved to be advantageous to install a finely divided foam as the filter bed and to pass the exchange solution through this filter.

Suitable for the process according to the invention are agglomerated foams, since the surface area available here is particularly high.

The adsorption should preferably be carried out at a pH-value in the range 2-12, preferably 4-10. The adjustment of the pH-value can then be carried out using a buffer solution. In the case of precipitation of metal hydroxides, these can likewise be physically adsorbed on the foam and thus separated. As buffer, known buffer solutions in this pH range can be selected, for example citric acid-buffer or phosphate-buffer.

After the exchange capacity of the polyurethane foam used according to the invention has been exhausted, extraction can optionally be achieved with an acid or a complexing agent. The functionalized foam material is
It can be used again after playback.

If the regeneration of the foam material is not possible or only possible with difficulty, it can be thermally utilized without cost. Corresponding metals may optionally be included as alloying components in the blast furnace metal.

The adsorption of radioactive compounds, atoms or ions can lead to the collection of components that give rise to radioactivity. The volume concentration increase achieved thereby is high and economically advantageous. The PUR-foam material thus loaded can then optionally be embedded in concrete or permanently encapsulated. After that, final storage is possible.

The polyurethane foams according to the invention can also be used in the form of foam pads, especially for the adsorption of odor substances. Furthermore, they can be used in the manufacture of molded articles and daily necessities. Examples for this are fillings for soles, clothes hangers and liners, among others. The manufacture of these moldings also includes objects, such as clothes hangers, cabinet doors or Hinterschaum behind the armature in vehicles.

The adsorbent foams used according to the invention can preferably be used in the temperature range> 0 ° C. to 110 ° C., with only a limited lifetime expected at temperatures> 90 ° C. .

The polyurethane foam according to the invention is preferably open-cell, in order to ensure the largest possible surface area for the contact between the compounds (i) and / or (ii) and the substance to be adsorbed. .

Furthermore, it is advantageous to control the hydrophilicity of polyurethane foams, especially those containing compound (i), so that the optimization of the foam in liquids containing harmful substances to be adsorbed. Allows for proper wetting. The hydrophilicity of polyurethane-foam material is, for example,
It can be increased by the use of polyetherols with a high content of ethylene oxide in the chain.

The polyurethane foam produced according to the method according to the invention preferably has a content of 10
˜800 kg / m ³ , particularly preferably 20 to 700 kg / m ³ and especially 40 to 6
It has a density of 0 kg / m ³ .

For the production of the polyurethanes according to the invention, the isocyanates are in the customary manner in the presence of compounds having at least two active hydrogen atoms, a blowing agent and optionally catalysts and / or auxiliaries and / or additives. Reacted. Here, the compounds having at least two hydrogen atoms which are reactive with isocyanate groups and the blowing agents, catalysts and auxiliaries and / or additives mentioned below are often combined before the reaction to the so-called polyol component. , And these are contacted with the isocyanate component.

Possible starting products for carrying out the process according to the invention, namely isocyanates, compounds having at least 2 active hydrogen atoms, blowing agents and optionally catalysts and / or auxiliaries and / or additives, are Can include: Isocyanates, preferably polyisocyanates, particularly preferably diisocyanates, preferably organic diisocyanates, in which the usual and known (cyclic) aliphatic polyisocyanates and aromatic polyisocyanates are used. You can Examples of aromatic polyisocyanates are 2,4- and 2,6-toluylene diisocyanate (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethane-diisocyanate (MDI), polyphenylene- Polymethylene-polyisocyanate (crude-MDI) and 1,5-naphthylene diisocyanate.

Examples of (cyclic) aliphatic di- or tri-isocyanates are tetramethylene diisocyanate-1,4, hexamethylene diisocyanate-1,6, isophorone diisocyanate, 2-methyl-pentamethylene diisocyanate, 2,2,2. 4-
Or 2,4,4-trimethyl-1,6-hexamethylene-diisocyanate, 2
-Butyl-2-ethyl-pentamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane, isocyanatopropyl-cyclohexyl isocyanate, xylylene diisocyanate, tetramethylxylyl Diisocyanate, bis- (
4-isocyanatocyclohexyl) -methane, lysine ester isocyanate,
1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, 4-isocyanatomethyl-1,8-octamethylene diisocyanate and mixtures thereof or oligo- or polyisocyanates prepared therefrom.

The oligo- or polyisocyanates can be urethane-, allophanate-, urea-, biuret-, from the listed di- or triisocyanates or mixtures thereof.
It can be prepared by conjugation via a uretdione-, amide-, isocyanurate-, carbodiimide-, uretoimine-, oxadiazinetrione- or iminooxadiazinedione-structure.

The isocyanates mentioned may be modified, for example by the incorporation of carbodiimide groups. Often polyisocyanates are also used in the form of prepolymers. This is a reaction product of the mentioned polyisocyanate and the polyol component. Mostly so-called isocyanate prepolymers are used, ie such reaction products of polyols and polyisocyanates having free isocyanate groups at the chain ends. Prepolymers and quasi-prepolymers and their preparation are generally known and described in many ways. Prepolymers having an NCO content in the range from 25 to 3.5% by weight are used in particular for the process according to the invention.

In a preferred embodiment of the process according to the invention, MDI and / or crude-MDI and biurets, isocyanurates, and aliphatic isocyanate-based allophanates are used as isocyanate components.

As compounds having at least two active hydrogen atoms, preferably polyester alcohols and particularly preferably 2-8, in particular 2-4, especially 2-3 functionalities and 1000-8500 g / mol, preferably 1000. Polyetherols having an average molecular weight in the range of ~ 6000 are used. The compounds having at least 2 active hydrogen atoms also include chain extenders and crosslinkers, which can optionally be used in combination. As chain extenders and crosslinkers, preferably 2- and 3-functional alcohols having a molecular weight of less than 1000 g / mol and especially in the range from 60 to 150 are used. Examples are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol with a molecular weight below 1000, polypropylene glycol with a molecular weight below 1000 and / or butanediol-1,4. Diamines can also be used as crosslinking agents. If chain extenders and crosslinkers are used, their amounts are
It is preferably up to 5% by mass with respect to the mass of isocyanate.

As catalysts for the production of polyurethane foams according to the invention, the customary and known polyurethane-forming catalysts can be used. For example organotin compounds such as tin diacetate, tin dioctoate, dialkyl tin dilaurates and / or
Or a strongly basic amine such as triethylamine, pentamethyldiethylenetriamine, tetramethyldiaminoethylether, 1,2-dimethylimidazole,
Dimethylcyclohexylamine, dimethylbenzylamine or preferably triethylenediamine. The catalyst is preferably 0.01% based on the weight of the isocyanate.
It is used in an amount of -5% by weight, preferably 0.05-2% by weight.

As blowing agent for the production of polyurethane foams, isocyanate groups and water which reacts under liberation of carbon dioxide are preferably used. Physically acting blowing agents such as or with water, for example hydrocarbons such as n-pentane, isopentane or cyclopentane, or halogenated hydrocarbons such as tetrafluoroethane, pentafluoropropane, heptafluoro. Propane, pentafluorobutane, hexafluorobutane, dichloro-monofluoroethane or acetals such as methylal can also be used. In that case, the amount of the physical blowing agent is preferably 1 to the mass of the compound having at least two active hydrogen atoms.
It is in the range of 15% by weight, in particular 1-10% by weight, the amount of water preferably being 0.5-
It is in the range of 10% by weight, especially 1 to 5% by weight.

As auxiliaries and / or additives, for example, surface-active substances, foam stabilizers, foam regulators, external and internal mold release agents, fillers, pigments, hydrolysis-protective agents and fungistatic and true additives Substances that act bacterially can be used.

In the production of the polyurethane foam according to the present invention, the polyisocyanate and the compound having at least two hydrogen atoms reactive with the isocyanate group are preferably the equivalent ratio of the isocyanate group and the total of active hydrogen atoms. Is 0.7 to 1.8: 1,
It is preferably reacted in an amount such that it is 0.7 to 1.2: 1.

The production of polyurethane foams is preferably carried out by the one-shot method, for example using high-pressure or low-pressure techniques. The foam material can be produced in open or closed molds or by continuous application of the reaction products onto a conveyor belt for the production of foam blocks.

It is particularly advantageous to be processed by the so-called two-component method, in which the polyol and isocyanate components are prepared and foamed together, as explained above. The ingredients are preferably 15-90 ° C, preferably 20-60 ° C.
And particularly preferably mixed at a temperature in the range of 20 to 35 ° C. and applied in a mold or on a conveyor belt. The temperature in the mold is usually 20-110 ° C,
It is preferably in the range of 30 to 60 ° C and particularly preferably 35 to 55 ° C.

In the case of the direct addition of compounds (i) or (ii) already in the production of polyurethane foams, these can be added to the polyol component as well as the isocyanate component. Preferably, (i) or (ii) is added to the polyol component.

[0056]   The invention shall be illustrated by the following examples.

Example 1 Preparation of Polyurethane Foams For the preparation of polyurethane foams, the foam recipes listed in Table 1 were used. The isocyanate and polyol components were foamed with an index of 100.

[0058] Table 1: Recipe for the polyurethane foam produced from Example 1.

[0059]

[Table 1]

Lupranol ^(R) 2040, (BASF Corporation), glycerin-based polyetherol, OHZ = 28.0 Lupranol ^(R) 2047, (BASF Corporation), glycerin-based polyetherol, OHZ = 42.0 Lupranol ^{(R) )} 3402, (BASF Corporation), ethylenediamine-based polyetherol, OHZ = 470 Lupragen ^(R) N 201, (BASF Corporation), (33% DAB in dipropylene glycol)
CO solution) Lupragen ^(R) N 206, (BASF Corporation), bis (dimethylaminoethyl) ether 70% in dipropylene glycol Tegostab B 8418 (Goldschmidt), silicone stabilizer B 620/1 ^(R) , Elastogran, Lupranat MI, Lupranat M20W and Lupranol 2030
Consisting prepolymer Lupranat ^(R) M20W, ^(BASF Corporation), after oligomeric MDI production, the foam was processed into flocs in a mill.

Example 2 Immobilization of Polyethyleneimine The foam flock produced in Example 1 was shaken with a 5% aqueous Lupasol solution for 15 minutes, using 25 ml of Lupasol solution per gram of foam. The foam flocs were subsequently filtered off, heat-treated at 100 ° C. for 16 hours, and washed with distilled water after the heat-treatment.

A) Lupasol ^(R) FG (BASF Corporation, polyethyleneimine with MG 800 g / mol) b) Lupasol ^(R) PR (BASF Corporation, polyethyleneimine with MG 2000 g / mol) c) Lupasol ^{(R )} WF (BASF Corporation, polyethyleneimine) example 3 having a MG 25 000 g / mol: a foam flock produced in immobilization example 1 of polyethyleneimine, 1 with 20% Lupasol ^(R) WF aqueous solution
Shake for 5 minutes, using 25 ml of solution per gram of foam material. The foam flocs were subsequently filtered off, heat-treated at 100 ° C. for 16 hours, and washed with distilled water after the heat-treatment.

[0063] Example 4: The foam flock produced in immobilization Example 1 polyethyleneimine, 20% acetone soluble Lupasol ^(R) WF
Shake in solution for 15 minutes, using 25 ml of solution per gram of foam. Subsequently, the foam flocs were filtered off, heat-treated at 100 ° C. for 16 hours, and washed with distilled water after the heat-treatment.

[0064] Example 5: a foam flock produced in immobilization Example 1 of polyethyleneimine, 1 with 20% Lupasol ^(R) in P solution
Shake for 5 minutes, using 25 ml of solution per gram of foam material. The foam flocs were subsequently filtered off, heat-treated at 100 ° C. for 16 hours, and washed with distilled water after the heat-treatment.

[0065] Lupasol ^(R) P Example (BASF Corporation, polyethyleneimine having MG750000g / mol) 6: a foam flock produced in immobilization Example 1 of polyethyleneimine 10% acetonic Lupasol ^(R) WF
Shake in solution for 15 minutes, using 25 ml of solution per gram of foam. Subsequently, the foam flocs were filtered off, heat treated at 100 ° C. for 16 hours, and washed with distilled water after the heat treatment.

[0066] Example 7: a foam flock produced in immobilization Example 1 polyethyleneimine, 27% acetone soluble Lupasol ^(R) WF
Shake in solution for 15 minutes, using 25 ml of solution per gram of foam. The foam flocs were subsequently filtered off, heat-treated at 100 ° C. for 16 hours, and washed with distilled water after the heat-treatment.

Example 8: Immobilization of Polyvinylamine The foam flock produced in Example 1 was treated with an aqueous polyvinylamine solution (k-value = 88).
． It was shaken in 9) for 15 minutes, using 25 ml of polyvinylamine solution per gram of foam material. The foam flocs were subsequently filtered off, heat-treated at 100 ° C. for 16 hours, and washed with distilled water after the heat-treatment.

A) Concentration of polyvinylamine solution: 6.5% b) Concentration of polyvinylamine solution: 13% Example 9: Immobilization of polyvinylamine The foam flock produced in Example 1 was treated with an aqueous polyvinylamine solution (k- Value = 16
2) Shake in for 15 minutes, 2 g of polyvinylamine solution per 1 g of foam material
5 ml was used. The foam flocs were subsequently filtered off, heat-treated at 100 ° C. for 16 hours, and washed with distilled water after the heat-treatment.

A) Polyvinylamine Solution Concentration: 2.1% b) Polyvinylamine Solution Concentration: 4.2% Example 10: Use of Foams for Heavy Metal Depletion Produced in Example 2 for Heavy Metal Depletion The suitability of the foam material is quantified, for example, on the basis of the copper binding capacity, for which purpose 2 g of each foam material is used in
Shake for time. The copper concentration of the starting solution as well as the solution after contact with the foam flocs was determined photometrically using the Dr. Lange cuvette test. The following copper losses were obtained.

Foam Material from Example 2a) Cu 43.7 mg Foam Material from Example 2b) Cu 47.0 mg Foam Material from Example 2c) Cu 60.8 mg Example 11: Use of Foam Material for Heavy Metal Depletion Heavy Metal Impairment The suitability of the foams produced in Examples 3 and 4 for was exemplarily quantified on the basis of their copper binding capacity, for which purpose 1 g of each foam was added to 100 ml of a copper solution.
I shook it for 2 hours. The copper concentration of the starting solution as well as the solution after contact with the foam flocs was determined photometrically using the Dr. Lange cuvette test. The results are summarized in Table 2.

[0071] Table 2: Comparison of copper depletion of foams produced in Examples 3 and 4.

[0072]

[Table 2]

Example 12: Use of Foams for Heavy Metal Depletion The suitability of the foams produced in Examples 3 and 5 for heavy metal depletion was quantified, illustratively based on copper binding capacity, for which foams 1 g of each was shaken in 100 ml of a copper solution for 2 hours. The copper concentration of the starting solution as well as the solution after contact with the foam flocs was determined photometrically using the Dr. Lange cuvette test. The results are summarized in Table 3.

[0074] Table 3: Comparison of copper depletion of foams produced in Examples 3 and 5.

[0075]

[Table 3]

Example 13: Use of foams for heavy metal depletion The suitability of the foams produced in Examples 4, 6 and 7 for heavy metal depletion is illustratively quantified on the basis of their copper binding capacity, for which , Foam material 1g each, copper solution 100m
Shake in l for 2 hours. The copper concentration of the starting solution as well as the solution after contact with the foam flocs was determined photometrically using the Dr. Lange cuvette test. The results are summarized in Table 4.

[0077] Table 4: Comparison of copper depletion of foams produced in Examples 3 and 5.

[0078]

[Table 4]

Example 14: Use of foam for heavy metal depletion For the determination of the kinetics of heavy metal depletion, quantified by way of example for copper depletion, 0.1 g of the foam produced in Example 4 was Shake for various times in 100 ml of 250 ppm copper solution. The copper concentration of the starting solution as well as the solution after contact with the foam flocs was determined photometrically using the Dr. Lange cuvette test. The result is the fifth
It is summarized in the table.

[0080] Table 5: Kinetics of copper depletion in the foam produced in Example 4.

[0081]

[Table 5]

Example 15: Use of Foams for Heavy Metal Depletion The foam flock produced in Example 7 was used for the depletion of various heavy metals. For this, 1 g of each foam floc was shaken in 100 ml of a solution containing 3000 ppm heavy metal for 2 hours. The heavy metal concentration of the starting solution, as well as the solution after contact with foam flock, was measured using atomic absorption spectrometry. The results are summarized in Table 6.

[0083] Table 6: Depletion of various heavy metals by the foam produced in Example 7.

[0084]

[Table 6]

Example 16: Regeneration of foam material 15 g of foam flock prepared according to Example 5 was shaken in 375 ml of 2000 ppm copper chloride solution for 30 minutes. Subsequently, the supernatant copper solution was filtered off and the foam flocs were regenerated with 0.5n hydrochloric acid. 2000ppm copper chloride solution 375m
The foam flock was reloaded by reshaking in 1 (30 minutes). The results are summarized in Table 7.

[0086] Table 7: Impaired Copper Ions

[0087]

[Table 7]

Example 17: Use of Foam Material for Cleaning Paper Wastewater Foam flocs prepared according to Examples 7 and 9b were used for cleaning raw wastewater of a paper mill. For this, various amounts of foam were shaken in 50 ml of wastewater for 30 minutes. The quality of cleaning was measured photometrically with respect to the decrease in absorbance at a wavelength of 297 nm. The results are summarized in Table 8.

[0089] Table 8: Decrease in absorbance of papermaking wastewater

[0090]

[Table 8]

Example 18: Use of Foams for Dye Depletion In the wastewater of dyeing mills, there are mainly hydrolisiert dyes and therefore the reactive dye Remazol® Rot 198 (Dystar ^). Was previously dissolved in 0.01 N caustic soda solution and subsequently hydrolyzed in a water bath at 60 to 70 ° C. for about 3 hours.

For the depletion of the dye, 1 g of the foam flock from Example 7 was subsequently shaken with 50 ml of the dye solution for 5 hours, and the dye concentration of the solution was determined photometrically at the absorption maximum. Calibration was performed in the same test procedure with hydrolyzed dye. Diverse pH
The results of the Impairment of Remzol Rot 198 at -values are summarized in Table 9.

[0093] Table 9: Reactive dye Remazol Rot 198 concentration reduction

[0094]

[Table 9]

Example 19: Use of Foams for Dye Depletion In the wastewater of a dyeing plant, mainly hydrolyzed dyes are present and therefore the reactive dye Procion Blue MX-R (Fluka, CAS: 13324 -20-4) was dissolved in 0.01N caustic soda solution in advance and subsequently hydrolyzed in a water bath at 60 to 70 ° C. for about 3 hours.

To deplete the dyestuff, 1 g of the foam flock from Example 7 was subsequently shaken with 50 ml of dye solution for 6 hours and the dye concentration of the solution was determined photometrically at the absorption maximum. Calibration was performed in the same test procedure with hydrolyzed dye. The results are summarized in Table 10.

[0097] Table 10: Reactive Dye Procion Blue MX-R Concentration Reduction

[0098]

[Table 10]

Example 20: Use of Foams for Heavy Metal Depletion The suitability of the foams produced in Examples 8 and 9 for heavy metal depletion was quantified based on their copper binding capacity. For this purpose, 1 g of each foam material is used for 100 m of copper solution.
Shake in l for 2 hours. The copper concentration of the starting solution as well as the solution after contact with the foam flocs was determined photometrically using the Dr. Lange cuvette test. The results are summarized in Table 11.

[0100] Table 11: Comparison of copper depletion with foams produced in Examples 8 and 9.

[0101]

[Table 11]

Examples 21 to 31 correspond to the use of the foam according to the invention for the adsorption of odor substances.

A wide variety of optionally modified polyurethane foams were prepared and used for the adsorption of odorants according to the invention. The odor substance was simulated with a sour odor substance such as acetic acid. The adsorption of the model compounds was carried out at 25 ° C. in an air-conditioned cabinet (Klimaschrank) with a volume of 560 l. Inside the air conditioning cabinet, about 140-1
The model substance concentration was adjusted to 60 ppm V / V (V / V = concentration based on volume).
After addition of the foam material, the decrease in concentration was measured using gas chromatography. Lupr
The anols are various polyetherols made with different initiators and different ethylene oxide / propylene oxide amounts, and the Lupranats are various MDI-based products.

Example 21 Preparation of an aromatic polyurethane-soft foam material, hereinafter referred to as Comparative System 1, 1250.
105.2 g of A-component and 100 g of B-component using a stirrer at rpm.
(Index 100) was intensively mixed and the bubbling mixture was transferred into a plastic container having a volume of 5 l, the components being constituted as follows: Polyol-component: Lupranol 2040 ^(R) (BASF Corporation) 97.0 parts Lupranol 2047 ^(R) (BASF Corporation) 3.0 parts Water 3.3 parts Lupragen N 107 ^(R) (BASF Corporation) 0.6 parts Aminopropylimidazole 0.8 parts Tegostab B 8631 ^(R) (Goldschmidt) 0.5 Part B-Ingredients: Lupranat M 20 W ^(R) 42 parts Lupranat MES ^(R) 11 parts Lupranat MI ^(R) 47 parts Example 22 The production of an aromatic polyurethane-soft foam, hereinafter referred to as Comparative System 2, was 1250.
115.24 g of A-component and 100 g of B-component using a stirrer at rpm.
(Index 100) was mixed intensively and transferred by bubbling of the foaming mixture into a plastic container having a volume of 5 l, the components being constituted as follows: Polyol-component: Lupranol 2045 ^(R) ( BASF Corporation) 95 parts Lupranol 2047 ^(R) (BASF Corporation) 5 parts Lupranol 2030 ^(R) (BASF Corporation) 10.71 parts Water 3.45 parts Lupragen N 201 ^(R) (BASF Corporation) 0.48 parts Lupragen N 206 ^{( R)} (BASF Corporation) 0.13 parts Tetramethylhexamethylenediamine (BASF Corporation) 0.37 parts Tegostab B 8680 ^(R) (Goldschmidt) 0.1 parts B-ingredient: Lupranat M 20 W ^(R) 75 parts Lupranat MP 111 ^{(R )} is referred to as a comparative system 3 to 25 parts example 23 below, aliphatic polyurethane - the production of flexible foam, 1250
110 g of A-component and 100 g of B-component (index 110) are intensively mixed using a stirrer at rpm and the foaming mixture is transferred to a plastic container having a volume of 5 l, the components being Was composed of: Polyol-Component: Lupranol 2042 ^(R) (BASF Corporation) 56 parts Lupranol 2045 ^(R) (BASF Corporation) 35 parts Water 2 parts Lupragen N 209 ^(R) (BASF stock Company) 3rd division Lupragen N 201 ^(R) (BASF Corporation) 2nd division Lupragen N 206 ^(R) (BASF Corporation) 1st division Kosmos 29 ^(R) (Goldschmidt) 1st division Tegostab B 8680 ^(R) (BASF Corporation ⁾ ) 1 part B-component: Basonat HI 100 ^(R) (BASF Corporation) 100 parts Example 24 For the modification of the polyurethane foams of Examples 1 to 3, the foam is made of ethanolic KOH.
Impregnation with a solution (KOH content = 5%) and subsequent heat treatment at 100 ° C.

Example 25 For the modification of the polyurethane foams of Examples 1 to 3, the foam was made up with 5% acetone
It was impregnated with a polyethyleneimine solution and subsequently heat treated at 100 ° C.

Example 26 Plates of size 20 × 30 × 1 cm ³ were cut from the foam material produced in Example 2). Continuing this, about 140 to 160 ppm V / V (V / V =
It was placed in an air-conditioned cabinet with a volume of 560 l adjusted to an acetic acid concentration (volume-based concentration). The decrease in acetic acid concentration was followed by gas chromatography for a total of 5 minutes, and
It is shown graphically in. For comparison, the acetic acid concentrations obtained with Basotect® ⁽ BASF Corporation melamine-formaldehyde foam) and open-cell polystyrene foam are shown as a function of time.

Example 27 Plates with a size of 20 × 30 × 1 cm ³ were cut from the foam material produced in Examples 1), 2) and 3). This is continued in advance to about 140-160 ppm V
It was placed in an air-conditioned cabinet with a volume of 560 l adjusted to an acetic acid concentration of / V (V / V = concentration based on volume). The decrease in acetic acid concentration was followed by gas chromatography for a total of 5 minutes and is shown graphically in FIG.

Example 28 Two plates with a size of 20 × 30 × 1 cm ³ were cut from the aromatic polyurethane foam prepared in Example 1). One of these plates
Treated as described in Example 4). The results in FIG. 3 show the reduction in acetic acid concentration compared by gas chromatography of the modified and unmodified foams in comparison. At time t = 0, the acetic acid concentration was set to 100%.

Example 29 Two plates of size 20 × 30 × 1 cm ³ were cut from the aliphatic polyurethane foam prepared in Example 3). One of these plates
Treated as described in Example 4). The results in FIG. 4 show the reduction in acetic acid concentration compared by gas chromatography of the modified and unmodified foams in comparison.

Example 30 Two plates of size 20 × 30 × 1 cm ³ were cut from the aromatic polyurethane foam prepared in Example 1). One of these plates
Treated as described in Example 5). The results in FIG. 5 show the reduction in acetic acid concentration compared by gas chromatography of the modified and unmodified foams in comparison.

Example 31 Plates of various sizes were cut from the aromatic polyurethane foam prepared in Example 1) and the plates were treated as described in Example 5). The results in Figure 6 show a comparison of the decrease in acetic acid concentration followed by gas chromatography of modified foam pads of different sizes.

[Brief description of drawings]

[Figure 1]   The graph which shows the fall of the acetic acid concentration according to the contact time of various foaming materials.

[Fig. 2]   The graph which shows the fall of the acetic acid density | concentration according to the contact time of various foam materials.

FIG. 3 is a graph showing the decrease in acetic acid concentration as a function of contact time for unmodified polyurethane foam and polyurethane foam modified according to Example 4.

FIG. 4 is a graph showing the decrease in acetic acid concentration as a function of contact time for unmodified polyurethane foam and polyurethane foam modified according to Example 4.

FIG. 5 is a graph showing the decrease in acetic acid concentration as a function of contact time for unmodified polyurethane foam and polyurethane foam modified according to Example 5.

FIG. 6 is a graph showing the decrease in acetic acid concentration as a function of contact time for foams of different sizes modified according to Example 6.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08G 18/64 C08G 18/64 // (C08G 18/38 18/38 101: 00) 101: 00 (81 ) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, TR), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, G M, KE, LS, MW, MZ, SD, SL, SZ, TZ , UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY , B Z, CA, CH, CN, CR, CU, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT , RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Andreas Alt Germany Drever Ehlbrock 7 (72) Inventor Ulrich Troilling Bensheim Melibox Strasse 24 (72) Inventor Reiner Lamm Germany Ludwigshafen Feng Orange -Strasse 18 (72) Inventor Jürgen Decker Germany Speyer Martin-Luter-Strasse 8 (72) Inventor Ulrich Steierle Germany Heidelberg Gel Vinusweg 32 (72) Inventor Martin Kreiens Schmidt Germany Rhone Corfeitstrasse 22 (72) Inventor Villi Riegel Werckhauser Oberer Bachstraße, Federal Republic of Germany 54 (72) Inventor Werner Bertref, Federal Republic of Germany Viernheim Franz-Mark-Strasse 12 F-term (reference) 4G066 AA13B AA16B AB12B AC24C AC27B AC31B AC33B BA22 BA36 CA02 CA10 CA46 CA47 CA56 DA02 DA03 DA08 FA03 FA12 FA37 GA11 4J034 BA02 BA03 BA08 CA01 CA04 CA17 CE01 DA01 DA02 DD01 DG03 DG04 DH02 DP20 DR04 HA01 HA06 HA07 HB06 HB07 HB08 HB09 HC01 HC02 HC03 HC11 HC12 HC16 HC17 HC22 HC25 HC32 HC34 HC35 HC44 HC46 HC52 HC61 HC63 HC64 HC66 HC67 HC71 HC73 KA01 KB05 KC17 KD11 KE02 LA08 MA03 NA02 NA03 NA06 QB12 QB15 QB16 QB17 QC01 QD03 RA04 RA17

Claims (9)

[Claims] 1. In a polyurethane foam, (i) ethyleneimine, polyethyleneimine, polyvinylamine, polyvinylamine-copolymer, carboxymethylated polyethyleneimine, phosphonomethylated polyethyleneimine, quaternized polyethyleneimine and / or A polyurethane foam characterized in that it contains a dithiocarbamated polyethyleneimine or (ii) an alkali metal hydroxide and / or an alkaline earth metal hydroxide or a mixture of (i) and (ii). 2. The polyurethane foam according to claim 1, containing (i) covalently bonded to the polymer of the foam. 3. An alkali metal hydroxide and / or an alkaline earth metal hydroxide (ii) containing sodium hydroxide and / or potassium hydroxide,
The polyurethane foam material according to claim 1. 4. (i) and / or (ii) is 0.1 with respect to the mass of the foamed material.
The polyurethane foam material according to any one of claims 1 to 3, which comprises -80% by mass. 5. Use of a polyurethane foam according to any one of claims 1 to 4 for the adsorption of compounds, preferably odorants, heavy metal ions and / or dyes. 6. A method according to any one of claims 1 to 4 for producing a shaped body.
Use of the polyurethane foam described in the item. 7. A method for producing a polyurethane foam by the reaction of polyisocyanate and a compound having at least two hydrogen atoms reactive with isocyanate, comprising: (i) ethyleneimine, polyethyleneimine, polyvinylamine, polyvinylamine Copolymer, carboxymethylated polyethyleneimine, phosphonomethylated polyethyleneimine, quaternized polyethyleneimine and / or dithiocarbamate polyethyleneimine or (ii) alkali metal hydroxide and / or alkaline earth metal hydroxide or (i) and A process for producing a polyurethane foam, characterized in that the mixture consisting of (ii) is applied onto the surface of the foam. 8. The process according to claim 7, wherein the reaction is carried out in the presence of compounds (i) and / or (ii). 9. The process according to claim 7, wherein the polyurethane foam is impregnated with compound (i) or with a solution of compound (ii) after its production.